US7745348B2 - Manufacturing method of a semiconductor device - Google Patents
Manufacturing method of a semiconductor device Download PDFInfo
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- US7745348B2 US7745348B2 US11/228,419 US22841905A US7745348B2 US 7745348 B2 US7745348 B2 US 7745348B2 US 22841905 A US22841905 A US 22841905A US 7745348 B2 US7745348 B2 US 7745348B2
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- tantalum
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000010409 thin film Substances 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 58
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 43
- 238000000151 deposition Methods 0.000 claims description 41
- 238000000231 atomic layer deposition Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000005240 physical vapour deposition Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- CPRZXSNNOZTZIE-UHFFFAOYSA-N CC[Ta](CC)(CC)(CC)(CC)NC Chemical compound CC[Ta](CC)(CC)(CC)(CC)NC CPRZXSNNOZTZIE-UHFFFAOYSA-N 0.000 claims 1
- IYZDEOSFLDNSDK-UHFFFAOYSA-N CN(C)[Ta](N(C)C)N(C)C Chemical compound CN(C)[Ta](N(C)C)N(C)C IYZDEOSFLDNSDK-UHFFFAOYSA-N 0.000 claims 1
- MTHYQSRWPDMAQO-UHFFFAOYSA-N diethylazanide;tantalum(5+) Chemical compound CCN(CC)[Ta](N(CC)CC)(N(CC)CC)(N(CC)CC)N(CC)CC MTHYQSRWPDMAQO-UHFFFAOYSA-N 0.000 claims 1
- VSLPMIMVDUOYFW-UHFFFAOYSA-N dimethylazanide;tantalum(5+) Chemical compound [Ta+5].C[N-]C.C[N-]C.C[N-]C.C[N-]C.C[N-]C VSLPMIMVDUOYFW-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 18
- 230000004888 barrier function Effects 0.000 abstract description 15
- 125000002524 organometallic group Chemical group 0.000 abstract description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 83
- 230000008021 deposition Effects 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 239000010410 layer Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000010926 purge Methods 0.000 description 8
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910004479 Ta2N Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- BRUWTWNPPWXZIL-UHFFFAOYSA-N ethyl(methyl)azanide;tantalum(5+) Chemical compound [Ta+5].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C BRUWTWNPPWXZIL-UHFFFAOYSA-N 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910004537 TaCl5 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/45542—Plasma being used non-continuously during the ALD reactions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28568—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table the conductive layers comprising transition metals
Definitions
- the present invention relates to a manufacturing method of a semiconductor device.
- a diffusion barrier is frequently formed on an interior wall of a hole such as a contact hole or via hole, in order to prevent a metal such as copper used for a metal line from diffusing into underlying silicon and/or an adjacent oxide.
- the diffusion barrier must have conductivity, and typical examples thereof are titanium nitride (TiN), tungsten nitride (WN), and tantalum nitride (TaN).
- copper has no fine protective layer such as Al 2 O 3 , it shows poor adhesion to silicon dioxide (SiO 2 ), and it is difficult to dry etch.
- copper has a diffusion coefficient about 106 times higher than that of aluminum in silicon, and the diffused copper forms a deep energy level between band gaps.
- copper also has a high diffusion coefficient in SiO 2 , and accordingly, an insulating property between the copper lines may deteriorate. As a result, the high diffusion coefficient of Cu in silicon or SiO 2 may substantially deteriorate reliability of a semiconductor device.
- the diffusion barrier plays an important role in interconnections. Therefore, it is important to develop a technique that is capable of forming a fine diffusion barrier.
- TaN for example, is thermodynamically stable with copper. Accordingly, many methods have been developed to use a TaN thin film as a fine diffusion barrier during the copper line manufacturing process.
- TaN thin films generally have high thermal stability, excellent adhesion to the oxide layer, and a desirable diffusion barrier characteristic. Accordingly, TaN thin films are widely used as a diffusion barrier.
- the TaN thin film is formed of a TaN/Ta bi-layer with a thickness of 100 nm or more by a physical vapor deposition (PVD) method.
- PVD physical vapor deposition
- the TaN thin film must have a thickness of less than 5 nm.
- the TaN thin film generally cannot realize sufficiently uniform step coverage at such thicknesses.
- an atomic layer deposition (ALD) method has been developed.
- the ALD method employs a precursor (for example, a metal-organic precursor and a halogen compound such as TaCl 5 ) to form or deposit a TaN thin film.
- a precursor for example, a metal-organic precursor and a halogen compound such as TaCl 5
- the TaN thin film may include a substantial amount of carbon. In this case, a low film density and high resistivity result, such that the copper lines may not have desired electric characteristics.
- the present invention has been made in an effort to provide a manufacturing method of a semiconductor device having advantages of reducing impurities and increasing density of a TaN thin film.
- An exemplary method of manufacturing a semiconductor device includes forming a substrate having a plurality of predetermined structures therein, and forming a TaN thin film on the substrate by plasma-enhanced atomic layer deposition (PEALD) using a plasma gas comprising a Ta precursor and a hydrogen source gas (e.g., H 2 ).
- the substrate generally contains a plurality of semiconductor devices (e.g., transistors, diodes, resistors, capacitors, etc.) therein and/or thereon.
- Another exemplary method of manufacturing a semiconductor device includes purging a reactor and a gas line, injecting a Ta precursor in the reactor to deposit a Ta-containing layer on a substrate, purging the reactor and the gas line again, supplying a hydrogen source gas (e.g., H 2 gas) by opening a hydrogen source gas valve connected to the reactor and gas line, forming a TaN thin film by supplying a plasma power to the reactor, and stopping the supply of the plasma power and the hydrogen source gas.
- a hydrogen source gas e.g., H 2 gas
- the Ta precursor may be selected from among pentakis(ethylmethylamino)tantalum (PEMAT), tertbutylimido(trisdiethylamide)-tantalum (TBTDET), pentakis(diethylamide)tantalum (PDEAT), and pentakis(dimethylamide)tantalum (PDMAT).
- PEMAT pentakis(ethylmethylamino)tantalum
- TBTDET tertbutylimido(trisdiethylamide)-tantalum
- PDEAT pentakis(diethylamide)tantalum
- PDMAT pentakis(dimethylamide)tantalum
- the first and second purging steps of the reactor and gas line may be respectively performed for 1 to 3 sec, and/or the plasma power may be supplied for a length of time of from 11 to 13 sec.
- An inert and/or nitrogen-containing gas (e.g., N 2 gas) may be further supplied to the reactor, and the plasma gas may therefore further comprise an inert and/or nitrogen-containing gas.
- the TaN film may be deposited at a temperature of 250° C. or higher.
- the manufacturing method may further include forming a metal line on the TaN thin film.
- the metal line may comprise copper, aluminum, and/or tungsten.
- the manufacturing method may further include depositing a seed copper layer on the TaN thin film and forming a copper line on the seed copper layer.
- the seed copper layer may be formed by PVD, ALD, or a CVD method.
- the manufacturing method may further include depositing Ta on the TaN thin film, before depositing a seed copper layer on the Ta and/or forming a copper line on the seed copper layer.
- the manufacturing method may further include forming a copper line on the TaN thin film in a dual damascene or single damascene pattern.
- FIG. 1 is a schematic diagram of an apparatus used in a manufacturing method of a semiconductor device according to an exemplary embodiment of the present invention, wherein the apparatus employs the PEALD method to deposit a TaN thin film.
- FIG. 2 is a depth profile of TaN thin films deposited by a thermal decomposition ALD method, obtained by XPS-analyzing with respect to various deposition temperatures.
- FIG. 3 illustrates results obtained in TaN thin films deposited by the thermal decomposition ALD method, in which certain gas component ratios are varied and in which the results are obtained by an AES analysis, assuming a total of component ratios to be 100.
- FIG. 4 illustrates a chemical composition analysis result for various kinds of plasma gases used in plasma processing performed for increasing density, decreasing resistivity and/or removing impurities in the TaN thin film deposited using PEMAT.
- FIG. 5 illustrates a variation of resistivity values of TaN thin films deposited using various plasma gases.
- FIG. 6 illustrates a variation of resistivity values depending on deposition temperatures with respect to a TaN thin film having a 320 ⁇ thickness after 400 cycles of plasma processing when H 2 is used as a plasma gas.
- FIG. 7 illustrates a composition analysis result of TaN thin films formed at various deposition temperatures using a plasma gas containing H 2 , obtained by an AES analysis.
- FIG. 8 illustrates step coverage of a TaN thin film deposited on a substrate containing a single pattern having a via hole with an opening width of 0.18 ⁇ m and an aspect ratio of 6:1, at a deposition temperature of 300° C., and by 200 cycles of plasma processing using an H 2 plasma gas, which is obtained by SEM analysis.
- any part such as a layer, film, area, or plate, is deposited on another part, it means the part is directly on the other part or above the other part with at least one intermediate part. Further, if any part is said to be deposited directly on another part, it means that there is no intermediate part, layer or structure between the two parts.
- FIG. 1 is a schematic diagram of apparatus used in manufacturing a semiconductor device according to an exemplary embodiment of the present invention, where the apparatus employs the PEALD method to deposit a TaN thin film.
- the thin film deposition apparatus includes storage tanks 11 , 12 , 13 , 14 , an 16 for storing process gases, mass flow controllers (MFCs) 21 , 22 , 23 , 24 , and 25 , valves 30 a and 30 b for controlling the process gas(ses) flowing from the storage tank, a reactor 1 for reacting the process gases controlled by the MFCs and valves (e.g., to deposit a film onto a substrate in the reactor), gas lines 17 in which these process gases flow, and purge gas lines 18 for purging the reactor 1 and the gas line 17 , using the vacuum pump 9 before or after a reaction.
- MFCs mass flow controllers
- the reactor 1 includes a shower head 4 for providing uniform flow 5 of the process gas (or gas mixture), and a susceptor 2 for supporting a substrate 3 therein. Also, the reactor 1 is coupled with an RF power supplying apparatus 8 for supplying a power. The RF power supplying apparatus 8 is also coupled with an RF matching box 7 for controlling a periodic supply of power. Accordingly, the plasma reaction can be synchronized to the gas flow 5 .
- the reactor 1 may form an oxide layer with a thickness of about 1,000 ⁇ on the silicon substrate 3 .
- Silicon substrate 3 may have a diameter of 200 mm, 300 mm, etc.
- the storage tank 16 supplies a Ta precursor (e.g., pentakis(ethylmethylamino)tantalum, or PEMAT) through the gas line 17 to the reactor 1 .
- the Ta precursor e.g., pentakis(ethylmethylamino)tantalum
- PEMAT a metal-organic precursor, and it may react with other processing gases introduced into the reactor 1 or to be deposited on the oxide layer.
- a TaN thin film may be formed on the upper surface of the oxide layer.
- the temperature is generally controlled in a range of from 200° C. to 350° C. (preferably from 250° C. to 350° C.).
- impurities may be removed from the TaN thin film by plasma-processing the same using a hydrogen source such as hydrogen gas, or a mixture of a hydrogen source and a nitrogen source such as a mixed gas of hydrogen and nitrogen, to reduce the resistivity and to increase the density of the thin film.
- the hydrogen and/or nitrogen source may comprise a substantially carbon- and oxygen-free compound such as ammonia (NH 3 ) or hydrazine (H 2 NNH 2 ).
- the hydrogen and/or nitrogen source may further include an inert gas, such as He or Ar, etc.
- the RF power supplying apparatus 7 is operated under a plasma power of 300 W and a frequency of 13.56 MHz to generate plasma. That is, depositing a TaN thin film using PEALD according to the invention includes introducing a Ta precursor (e.g., PEMAT) and forming a TaN thin film by plasma processing.
- a Ta precursor e.g., PEMAT
- PEALD generally includes a plurality of cycles, wherein each cycle includes (1) purging of the reactor and the gas line, (2) supplying a Ta precursor and depositing a Ta-containing layer on the substrate, (3) purging the reactor and the gas line, (4) introducing a hydrogen and/or nitrogen source into the reactor (e.g., opening the gas valves for H 2 and N 2 ), (5) supplying a plasma power to the reactor and performing plasma processing, and (6) stopping the plasma power and closing the gas valves.
- the purging and Ta precursor supplying steps are performed for 2 seconds, and the plasma processing is performed for 12 seconds.
- the invention will be described in greater detail with reference to FIGS. 2 to 8 , in which the TaN thin film deposited from a dialkylamidotantalum (PEMAT) precursor at a temperature higher than 250° C. by the PEALD method has excellent resistivity, thin film component, binding energy, and step coverage characteristics.
- PEMAT dialkylamidotantalum
- XPS X-ray photoelectron spectroscopy
- FIG. 2 is a depth profile of TaN thin films deposited by a thermal decomposition ALD method, obtained by XPS-analysis with respect to various deposition temperatures.
- a TaN thin film has a binding energy of 21.5 eV and 26.5 eV. It is also known that peaks appear at 21.9 eV for pure Ta (Ta 4f7/2), and at about 26.5 eV for tantalum oxide.
- peaks of the TaN thin film are stably observed at a similar range of binding energy.
- tantalum (Ta) is combined with nitrogen instead of oxygen. That is, according to the thermal decomposition ALD method, the binding property of the TaN thin film shows that Ta binds with oxygen at a deposition temperature of lower than 200° C., and with nitrogen at a deposition temperature of higher than 250° C. Therefore, the deposition processing generally should be performed at a temperature higher than 250° C. in order to obtain a stable TaN thin film.
- impurities and compositions of Ta and N in the TaN thin film are analyzed using an Auger electron spectroscopy (AES) method.
- AES Auger electron spectroscopy
- FIG. 3 illustrates a variation of component ratio of TaN thin films deposited by the thermal decomposition ALD method, which is obtained by an AES analysis assuming a total of component ratios to be 100.
- the composition As shown in FIG. 3 , regarding the composition, as the deposition temperature is increased, the oxygen content is decreased, and the Ta content and the nitrogen content are increased. This result is in concordance with the XPS analysis result of FIG. 2 . That is, at a deposition temperature of 250° C. or higher, Ta and nitrogen are combined to generate the TaN thin film (although, under certain conditions, the TaN thin film may have sufficient conductivity properties for some applications when formed at a temperature between 200° C. and 250° C.).
- FIG. 4 illustrates a chemical composition analysis result for various kinds of plasma gases and gas mixtures used in plasma processing the substrate having a Ta-containing layer thereon.
- plasma processing is generally performed for increasing film density and decreasing film resistivity by removing impurities in the TaN thin film deposited using a dialkylamidotantalum precursor such as PEMAT.
- the TaN thin film is deposited at a deposition temperature of 300° C. over 300 cycles according to the PEALD method. According to scanning electron microscopy (SEM) analysis, the TaN thin film has a thickness of about 0.8 A during each cycle, regardless of the particular plasma gas mixture.
- SEM scanning electron microscopy
- the TaN thin film contains impurities of oxygen and carbon at an atomic percentage of 10% or less each (carbon being ⁇ 10 at. %), and the nitrogen is at a relatively higher level. This is because, in the plasma processing, carbon is replaced by nitrogen to increase the nitrogen content, the replaced carbon bonds with hydrogen to form volatile hydrocarbons (and/or alkylamines) that are easily removed, and the oxygen impurity can be removed as H 2 O.
- the TaN thin film has oxygen impurities at a level of about 25 at. % and carbon impurities at about a 10 at. % level, both of which are relatively higher in comparison with the case of the mixed hydrogen and nitrogen source gasses, and nitrogen is present in an atomic percentage of about 40%. Therefore, it is understood that the impurities are more effectively removed from the TaN thin film when plasma processing is performed using source(s) of hydrogen and nitrogen (e.g., the mixed gas of H 2 and N 2 ).
- FIG. 5 illustrates a variation of resistivity values of TaN thin films deposited using various plasma gases. Resistivity in the TaN thin film is measured using a 4 point probe method.
- the TaN thin film has impurities of oxygen and carbon at relatively higher levels in comparison with using a mixed gas of H 2 and N 2 .
- the resistivity is considerably reduced to 7,000 ⁇ -cm. This is because the TaN phase generally changes according to the nitrogen content.
- nitrogen can be replaced with carbon to form an fcc-TaN phase, having a face-center edcubic structure.
- the fcc-TaN phase has a crystalline structure by which a resistivity may become more than 10,000 ⁇ -cm.
- the TaN thin film has about 40% nitrogen to form an hcp-Ta 2 N phase, that is, a Ta 2 N phase of a hexagonal close-packed lattice structure.
- the hcp-Ta 2 N has resistivity of about 300 ⁇ -cm. Accordingly, it is understood that, when only hydrogen is used as the plasma gas according to an exemplary embodiment of the present invention, the hcp-Ta 2 N may have a higher resistivity than that of a conventional hcp-Ta 2 N. This is because impurities such as oxygen may be present.
- FIG. 6 illustrates a variation of resistivity values depending on deposition temperatures with respect to a TaN thin film having a 320 ⁇ thickness after 400 cycles of plasma processes when H 2 is used as a plasma gas. As shown in FIG. 6 , the resistivity varies significantly according to the deposition temperature.
- the TaN thin film has a low resistivity of 960 ⁇ -cm when deposited at a temperature of about 350° C.
- FIG. 7 shows composition analyses (obtained by AES analysis) of TaN thin films formed at various deposition and/or processing temperatures using an H 2 plasma gas.
- the TaN thin film when the TaN thin film is processed under an H 2 gas plasma atmosphere, the TaN thin film has a relatively uniform nitrogen content (in a range of from 30% to about 40%), regardless of the deposition temperature.
- the TaN thin film has a relatively smaller oxygen content as the deposition temperature is increased (from (a) to (d)), and Ta and carbon contents become larger as the oxygen content becomes smaller.
- the resistivity increase primarily depends on the oxygen content rather than the carbon content in the TaN thin film.
- the nitrogen content may be constant regardless of the deposition temperature.
- the TaN phase may also be constant regardless of the deposition temperature.
- FIG. 8 illustrates step coverage of a TaN thin film deposited on a substrate having a single pattern thereon (e.g., a via hole pattern having an opening width of 0.18 ⁇ m and an aspect ratio of 6:1), at a deposition temperature of 300° C., using 200 cycles of plasma processing and an H 2 plasma gas.
- a single pattern thereon e.g., a via hole pattern having an opening width of 0.18 ⁇ m and an aspect ratio of 6:1
- the results in FIG. 8 were obtained by SEM analysis.
- the TaN thin film 10 has side coverage at locations 52 and 53 in the via hole of about 95% and bottom coverage at location 51 of about 80%.
- the TaN thin film has excellent step coverage.
- the resistivity, composition, binding property and step coverage characteristics of the TaN thin film to be used as a diffusion barrier for a copper line with a width of 65 nm or less in a semiconductor device is found to be as described below.
- the TaN thin film deposited by the thermal decomposition ALD method is found to have a stronger Ta-N binding strength as the deposition temperature is increased.
- the PEALD method when the plasma gas contains hydrogen and no nitrogen source, the TaN thin film has a much better resistivity characteristic than in the case where the plasma gas comprises H 2 and N 2 . That is, the TaN thin film has a low resistivity of 960 ⁇ -cm when deposited at 350° C. under an H 2 gas plasma atmosphere. The resistivity is mostly dependent on the oxygen content among the impurities.
- the TaN thin film has excellent step coverage of about 95% in the via-hole structure of a size of 0.18 ⁇ m and an aspect ratio of 6:1.
- the TaN thin film may be used as diffusion barrier such that a metal line may be formed on the TaN thin film.
- These metal lines may comprise copper, aluminum, or tungsten.
- a TaN thin film is formed as described above, and a seed copper layer may be deposited on the TaN thin film by a conventional technique (e.g., electroplating). Copper lines are then formed on the seed copper layer by a conventional technique (e.g., PVD).
- a conventional technique e.g., electroplating
- Ta may be deposited on the TaN thin film, prior to depositing a seed copper layer on the Ta.
- the copper line may then be formed on the seed copper layer by PVD, ALD, or CVD.
- the copper line may be formed in a dual damascene and/or a single damascene pattern.
- the substrate may have an upper (or exposed) insulator layer containing a predetermined dual damascene and/or a single damascene pattern therein.
- the TaN thin film may provide a diffusion barrier function for the copper line of any pattern in the single and dual damascene patterns.
- the method of manufacturing a semiconductor device generally employs a PEALD method, using an organometallic Ta precursor such as PEMAT to form a TaN thin film.
- an organometallic Ta precursor such as PEMAT
- a conformal TaN diffusion barrier may be formed at a temperature higher than 250° C. so that impurities are reduced and density is increased in the TaN thin film.
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US7595270B2 (en) * | 2007-01-26 | 2009-09-29 | Asm America, Inc. | Passivated stoichiometric metal nitride films |
WO2009129332A2 (en) | 2008-04-16 | 2009-10-22 | Asm America, Inc. | Atomic layer deposition of metal carbide films using aluminum hydrocarbon compounds |
DE102008035235B4 (en) * | 2008-07-29 | 2014-05-22 | Ivoclar Vivadent Ag | Device for heating molded parts, in particular dental ceramic molded parts |
US10002936B2 (en) | 2014-10-23 | 2018-06-19 | Asm Ip Holding B.V. | Titanium aluminum and tantalum aluminum thin films |
US10672652B2 (en) * | 2018-06-29 | 2020-06-02 | Taiwan Semiconductor Manufacturing Co., Ltd. | Gradient atomic layer deposition |
CN114864662B (en) * | 2022-04-25 | 2023-04-28 | 湖南楚微半导体科技有限公司 | Schottky structure based on TiN/TaN template and preparation method and application thereof |
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